CN110229961A - A kind of technique leaching electrolytic manganese residues and manganese tailing using titanium white waste acid - Google Patents
A kind of technique leaching electrolytic manganese residues and manganese tailing using titanium white waste acid Download PDFInfo
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- CN110229961A CN110229961A CN201910265742.XA CN201910265742A CN110229961A CN 110229961 A CN110229961 A CN 110229961A CN 201910265742 A CN201910265742 A CN 201910265742A CN 110229961 A CN110229961 A CN 110229961A
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- Prior art keywords
- manganese
- liquid
- iron oxide
- leachate
- titanium white
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 48
- 239000011572 manganese Substances 0.000 title claims abstract description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 235000010215 titanium dioxide Nutrition 0.000 title claims abstract description 34
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 25
- 238000002386 leaching Methods 0.000 title claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000007788 liquid Substances 0.000 claims abstract description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 14
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 238000012797 qualification Methods 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 37
- 238000004519 manufacturing process Methods 0.000 claims description 14
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 10
- 239000011656 manganese carbonate Substances 0.000 claims description 10
- 235000006748 manganese carbonate Nutrition 0.000 claims description 10
- 229940093474 manganese carbonate Drugs 0.000 claims description 10
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 10
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000011449 brick Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical group [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- 239000001034 iron oxide pigment Substances 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 239000001166 ammonium sulphate Substances 0.000 abstract 1
- 238000011161 development Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- -1 manganous fluoride Magnesium Chemical compound 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052935 jarosite Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- KQFUCKFHODLIAZ-UHFFFAOYSA-N manganese Chemical compound [Mn].[Mn] KQFUCKFHODLIAZ-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of techniques that electrolytic manganese residues and manganese tailing are leached using titanium white waste acid, specifically includes the following steps: carrying out liquid phase crushing to electrolytic manganese residues obtains leached mud and leachate by concentrator separating and concentrating；Leached mud pass through and alkaline matter in and colloidization reaction, manganese tailing is added into leachate, leachate is obtained into the qualification without solid particle except liquid before iron, obtained iron oxide yellow or iron oxide red slurry by filters pressing, is filtered with filter press.The invention has the advantages that: leachate liquefied ammonia, ammonium hydroxide or carbonic acid hydrogen ammonium produce iron oxide pigment, solve conventionally produced EMD as the heavy iron of precipitating reagent, and liquid ammonium sulphate content high impurity content is low after heavy manganese, realizes low energy consumption, zero-emission.Agricultural ammonium sulfate is produced using MVR evaporation, has saved a large amount of steam and equipment, the leachate liquid after reaction is greater than 60g/L, simple process, stabilization, strong operability containing manganese.
Description
Technical field
The present invention relates to new environment-protective process technical fields, in particular to a kind of utilization titanium white waste acid to leach electrolytic manganese residues and manganese
The technique of tailing.
Background technique
Manganese ore industry fast development promotes economic rapid growth, but manganese tailing hoards the spare time for also increasing promoter manganese
Damage is set and lost, the waste of the raw material of industry is caused.Such as in electrolytic manganese production process, every production 1t electrolytic manganese metal need to consume manganese ore
7-8t of stone generates 5-6t of electrolytic manganese residues.Currently, only the electrolytic manganese waste residue whole nation has just hoarded about 20,000,000 t, electrolytic manganese residues are such as pressed
In using manganese content be 1%-3% calculate, be dropped or flow damage promoter manganese be about 20-60 ten thousand t.If do not improved manganese ore
Technique of preparing, reinforce manganese tailing development and utilization, with the increase of manganese tailing amount, the environment and ecological problem of initiation will be got over
Come more, tailing, which is hoarded, causes mining area ecological environment constantly to deteriorate.Large scale mining and utilization with mineral resources, mining area ring
Border system is affected and destroys, and the ecological environment problem that a large amount of manganese tailings cause also is got worse.It is mainly manifested in: 1. manganese tail
In mine harmful element pollute environment, due to waste residue for a long time hoard, some harmful elements by soil layer permeate, into surface water with
Underground water forms pollution sources difficult to degrade and reluctant, and river biology can be made to disappear, and groundwater resources are scrapped, harmful to human
Health；2. destroyed area is ecological, due to mine soil lack nutriment, and the content of beary metal such as manganese, iron are excessively high can be to root system of plant
Murder by poisoning is generated, the natural vegetation restoration time on discarded ground is extended, while causing biology to migrate and being obstructed, bio-diversity reduces；
3. damage to land provides, afield intermountain can not be handled a large amount of manganese tailing manganese slag muck products, not only take up agriculture plantation, also induction mudstone
The geological disasters such as stream；4. causing other social concerns, mine waste residue is hoarded, and increases the expenses such as enterprise's land acquisition and place disposition
And increase production cost, and largely occupy agriculture plantation, intensify the contradiction between enterprise and resident.The ecology of manganese ore industry development
While environment capacity evaluation and analysis promotes rapid economic development using promoter manganese, between the demanganization level of resources utilization and industrial benefit
Outside relationship, there is also Resources Reserves to the stress Game Relationship of environment.And while eco-environmental quality index gradually decreases,
Manganese ore industrial harmonization degree is gradually increased, and illustrates that the development of Guangxi manganese mining industry is in be gradually reduced trend to the dependence of ecological environment.
It develops a circular economy, builds Ecological Park, carries out pollution-free industry, the destruction to ecological environment can be gradually decreased.
Titanium white production enterprise uses Titanium White Production By Sulfuric Acid Process, and Titanium White Production By Sulfuric Acid Process can generate a large amount of titanium white
Spent acid.If dealt with improperly, these titanium white waste acids can cause local environment seriously to pollute.Currently, the processing side of titanium white waste acid
Formula is roughly divided into two kinds, and first way is in spent acid and quick lime and will to generate calcium sulfate precipitation, then puts neutralization slag muck
To cinder field；The second way is to be concentrated in vacuo spent acid by steam heating, and acid-spending strength is improved to after 70%, then with
98% concentrated sulfuric acid carries out complex acid, returns to titanium dioxide acid hydrolysis workshop section and uses.The first processing mode can generate a large amount of sulfate slag, due to
Impurity content is more, non-recovery utility value, these waste residues can only discard stockpiling, and occupy a large amount of land resource.Second
Kind of processing mode then complex process, cost recovery is high, therefore not all titanium white production enterprise all has ready conditions application.Cause
This, each titanium white production enterprise needs to find more economical reasonable titanium white waste acid recovery and treatment method, can become give up into
Treasured realizes the utilization again of resource.
Summary of the invention
The purpose of the present invention is to provide a kind of techniques that electrolytic manganese residues and manganese tailing are leached using titanium white waste acid, to solve
The problems mentioned above in the background art.
In order to solve the above technical problems, technical solution provided by the invention are as follows: a kind of to leach electrolytic manganese using titanium white waste acid
The technique of slag and manganese tailing, which is characterized in that specifically includes the following steps:
1) liquid phase crushing is carried out to electrolytic manganese residues using dispersion machine, by the smashed electrolytic manganese residues of liquid phase and Titanium white waste sulfuric acid
Hybrid reaction is carried out, leaches each valence state manganese inside electrolytic manganese residues completely with ferrous ion using the residual acid inside Titanium white waste sulfuric acid
Then ion passes through concentrator separating and concentrating, obtains leached mud and leachate；
2) leached mud, which passes through, reacts in alkaline matter with colloidization, then adds the solidification production of cement and lime mixed-forming and build
Build environmental protection brick and haydite；
3) manganese tailing is added into leachate obtained by step 1), obtains ferrous ion and sulfuric acid content and all meets technique requirement
Leachate；
4) gained leachate in step 3) is obtained into the qualification without solid particle except liquid before iron by filters pressing, held in reaction
Water and iron oxide crystal seed are added in device, is then heated to 60-100 DEG C, adds the liquid before removing iron purified, while being added and containing ammonia
Liquid precipitation goes out iron oxide red, controls reaction kettle liquid pH value 2-5.5, and temperature controls between 60-100 DEG C, when reaction stops
Between control at 2-5 hours, obtain iron oxide yellow or iron oxide red slurry after the reaction was completed, then filter；
5) the filtered solid convection drying of step 4) is obtained into iron oxide yellow, after the filtered solid calcining of step 4)
Obtain iron oxide red, ferrous sulfate and reduction reaction containing ammonia liquid added into the filtered solid of step 4) and is made the transition, after obtain
Iron oxide black；
6) it is removed to step 4) and sulfide reaction removing heavy metals is added in the filtered liquid of iron, then react deliming with fluoride
Magnesium is added after ammonium hydrogen carbonate adjusts pH value 6.8-7.5 and reacts 2 hours, be aged 1-3 hours, then use filter press after solid-liquid
Filtering obtains manganese carbonate precipitating, then dry LITHIUM BATTERY manganese carbonate；Filtrate obtains liquid before qualified ammonium sulfate evaporates；Then
Ammonium sulfate is recycled using MVR evaporative crystallization.
As a preferred embodiment, the alkaline matter in the step 2) is red mud.
As a preferred embodiment, described is one of liquefied ammonia, ammonium hydroxide, ammonium hydrogen carbonate containing ammonia liquid.
As a preferred embodiment, the sulfide in the step 6) is manganese sulfide, the fluoride in the step 6)
For manganous fluoride.
The invention has the advantages that: this technique realizes electrolytic manganese residues, manganese tail using Titanium white waste sulfuric acid leaching enrichment manganese ion
Manganese manganese slag is less than 0.001% after mine manganese content only leaches, for manganese Making Use of Tailings synthetical recovery open one it is new profitable
Industrial routes.Leachate liquefied ammonia, ammonium hydroxide or carbonic acid hydrogen ammonium produce iron oxide pigment, solve tradition as the heavy iron of precipitating reagent
Technique produces EMD, and the irretrievable pollution of the sodium jarosite and goethite that iron purification generates and EMD are due to infusion solution purification
The problems such as impure bring EMD purity is low.Liquid hold-up high impurity content is low after heavy manganese, can be used as ammonium sulfate production raw material, realizes
Low energy consumption, zero-emission.Agricultural ammonium sulfate is produced using MVR evaporation, has saved a large amount of steam than the crystallization of traditional handicraft high temperature evaporation
And equipment.Leachate liquid after reaction is greater than 60g/L, simple process, stabilization, strong operability containing manganese.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Illustrate the present invention with specific embodiment below, is not limitation of the present invention.
Embodiment 1
A kind of technique leaching electrolytic manganese residues and manganese tailing using titanium white waste acid, which is characterized in that specifically include following step
It is rapid:
1) liquid phase crushing is carried out to electrolytic manganese residues using dispersion machine, by the smashed electrolytic manganese residues of liquid phase and Titanium white waste sulfuric acid
Hybrid reaction is carried out, leaches each valence state manganese inside electrolytic manganese residues completely with ferrous ion using the residual acid inside Titanium white waste sulfuric acid
Then ion passes through concentrator separating and concentrating, obtains leached mud and leachate；
2) leached mud, which passes through, reacts in alkaline matter with colloidization, then adds the solidification production of cement and lime mixed-forming and build
Build environmental protection brick and haydite；
3) manganese tailing is added into leachate obtained by step 1), obtains ferrous ion and sulfuric acid content and all meets technique requirement
Leachate；
4) gained leachate in step 3) is obtained into the qualification without solid particle except liquid before iron by filters pressing, held in reaction
Water and iron oxide crystal seed are added in device, is then heated to 60 DEG C, adds the liquid before removing iron purified, while being added and containing ammonia liquid
It is settled out iron oxide red, controls reaction kettle liquid pH value 5.5, at 60 DEG C, reaction time is small 5 in control for temperature control
When, iron oxide yellow or iron oxide red slurry are obtained after the reaction was completed, are then filtered；
5) the filtered solid convection drying of step 4) is obtained into iron oxide yellow, after the filtered solid calcining of step 4)
Obtain iron oxide red, ferrous sulfate and reduction reaction containing ammonia liquid added into the filtered solid of step 4) and is made the transition, after obtain
Iron oxide black；
6) it is removed to step 4) and manganese sulfide reaction removing heavy metals is added in the filtered liquid of iron, then react deliming with manganous fluoride
Magnesium is added after ammonium hydrogen carbonate adjusts pH value 6.8 and reacts 2 hours, be aged 3 hours, then filtered with filter press after solid-liquid,
Manganese carbonate precipitating is obtained, then dry LITHIUM BATTERY manganese carbonate；Filtrate obtains liquid before qualified ammonium sulfate evaporates；Then it utilizes
MVR evaporative crystallization recycles ammonium sulfate.
Embodiment 2
A kind of technique leaching electrolytic manganese residues and manganese tailing using titanium white waste acid, which is characterized in that specifically include following step
It is rapid:
1) liquid phase crushing is carried out to electrolytic manganese residues using dispersion machine, by the smashed electrolytic manganese residues of liquid phase and Titanium white waste sulfuric acid
Hybrid reaction is carried out, leaches each valence state manganese inside electrolytic manganese residues completely with ferrous ion using the residual acid inside Titanium white waste sulfuric acid
Then ion passes through concentrator separating and concentrating, obtains leached mud and leachate；
2) leached mud, which passes through, reacts in alkaline matter with colloidization, then adds the solidification production of cement and lime mixed-forming and build
Build environmental protection brick and haydite；
3) manganese tailing is added into leachate obtained by step 1), obtains ferrous ion and sulfuric acid content and all meets technique requirement
Leachate；
4) gained leachate in step 3) is obtained into the qualification without solid particle except liquid before iron by filters pressing, held in reaction
Water and iron oxide crystal seed are added in device, is then heated to 100 DEG C, adds the liquid before removing iron purified, while being added and containing ammoniacal liquor
Body is settled out iron oxide red, controls reaction kettle liquid pH value 2, at 100 DEG C, reaction time is small 2 in control for temperature control
When, iron oxide yellow or iron oxide red slurry are obtained after the reaction was completed, are then filtered；
5) the filtered solid convection drying of step 4) is obtained into iron oxide yellow, after the filtered solid calcining of step 4)
Obtain iron oxide red, ferrous sulfate and reduction reaction containing ammonia liquid added into the filtered solid of step 4) and is made the transition, after obtain
Iron oxide black；
6) it is removed to step 4) and manganese sulfide reaction removing heavy metals is added in the filtered liquid of iron, then react deliming with manganous fluoride
Magnesium is added after ammonium hydrogen carbonate adjusts pH value 7.5 and reacts 2 hours, be aged 1 hour, then filtered with filter press after solid-liquid,
Manganese carbonate precipitating is obtained, then dry LITHIUM BATTERY manganese carbonate；Filtrate obtains liquid before qualified ammonium sulfate evaporates；Then it utilizes
MVR evaporative crystallization recycles ammonium sulfate.
Embodiment 3
A kind of technique leaching electrolytic manganese residues and manganese tailing using titanium white waste acid, which is characterized in that specifically include following step
It is rapid:
1) liquid phase crushing is carried out to electrolytic manganese residues using dispersion machine, by the smashed electrolytic manganese residues of liquid phase and Titanium white waste sulfuric acid
Hybrid reaction is carried out, leaches each valence state manganese inside electrolytic manganese residues completely with ferrous ion using the residual acid inside Titanium white waste sulfuric acid
Then ion passes through concentrator separating and concentrating, obtains leached mud and leachate；
2) leached mud, which passes through, reacts in alkaline matter with colloidization, then adds the solidification production of cement and lime mixed-forming and build
Build environmental protection brick and haydite；
3) manganese tailing is added into leachate obtained by step 1), obtains ferrous ion and sulfuric acid content and all meets technique requirement
Leachate；
4) gained leachate in step 3) is obtained into the qualification without solid particle except liquid before iron by filters pressing, held in reaction
Water and iron oxide crystal seed are added in device, is then heated to 80 DEG C, adds the liquid before removing iron purified, while being added and containing ammonia liquid
It is settled out iron oxide red, controls reaction kettle liquid pH value 4, at 80 DEG C, reaction time was controlled at 4 hours for temperature control,
Iron oxide yellow or iron oxide red slurry are obtained after the reaction was completed, are then filtered；
5) the filtered solid convection drying of step 4) is obtained into iron oxide yellow, after the filtered solid calcining of step 4)
Obtain iron oxide red, ferrous sulfate and reduction reaction containing ammonia liquid added into the filtered solid of step 4) and is made the transition, after obtain
Iron oxide black；
6) it is removed to step 4) and manganese sulfide reaction removing heavy metals is added in the filtered liquid of iron, then react deliming with manganous fluoride
Magnesium is added after ammonium hydrogen carbonate adjusts pH value 7.2 and reacts 2 hours, be aged 2 hours, then filtered with filter press after solid-liquid,
Manganese carbonate precipitating is obtained, then dry LITHIUM BATTERY manganese carbonate；Filtrate obtains liquid before qualified ammonium sulfate evaporates；Then it utilizes
MVR evaporative crystallization recycles ammonium sulfate.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (4)
1. a kind of technique for leaching electrolytic manganese residues and manganese tailing using titanium white waste acid, which is characterized in that specifically includes the following steps:
1) liquid phase crushing is carried out to electrolytic manganese residues using dispersion machine, the smashed electrolytic manganese residues of liquid phase and Titanium white waste sulfuric acid is carried out
Hybrid reaction, using inside Titanium white waste sulfuric acid it is residual acid and ferrous ion leach completely each valence state manganese inside electrolytic manganese residues from
Then son passes through concentrator separating and concentrating, obtains leached mud and leachate；
2) leached mud, which passes through, reacts in alkaline matter with colloidization, then adds the solidification production of cement and lime mixed-forming and build ring
Protect brick and haydite；
3) manganese tailing is added into leachate obtained by step 1), obtains the leaching that ferrous ion and sulfuric acid content all meet technique requirement
Liquid out；
4) gained leachate in step 3) is obtained into the qualification without solid particle except liquid before iron, in reaction vessel by filters pressing
Water and iron oxide crystal seed is added, is then heated to 60-100 DEG C, adds the liquid before removing iron purified, while being added and containing ammonia liquid
It is settled out iron oxide red, controls reaction kettle liquid pH value 2-5.5, temperature controls between 60-100 DEG C, and reaction time exists
Control obtained iron oxide yellow or iron oxide red slurry after the reaction was completed, and then filtered at 2-5 hours；
5) the filtered solid convection drying of step 4) is obtained into iron oxide yellow, will be obtained after the filtered solid calcining of step 4)
Iron oxide red adds ferrous sulfate and reduction reaction containing ammonia liquid into the filtered solid of step 4) and makes the transition, after aoxidized
It is iron black；
6) it is removed to step 4) and sulfide reaction removing heavy metals is added in the filtered liquid of iron, then react removing calcium and magnesium with fluoride,
After solid-liquid, it is added after ammonium hydrogen carbonate adjusts pH value 6.8-7.5 and reacts 2 hours, be aged 1-3 hours, then with filter press mistake
Filter obtains manganese carbonate precipitating, then dry LITHIUM BATTERY manganese carbonate；Filtrate obtains liquid before qualified ammonium sulfate evaporates；Then sharp
Ammonium sulfate is recycled with MVR evaporative crystallization.
2. a kind of technique for being leached electrolytic manganese residues and manganese tailing using titanium white waste acid according to claim 1, feature are existed
In: the alkaline matter in the step 2) is red mud.
3. a kind of technique for being leached electrolytic manganese residues and manganese tailing using titanium white waste acid according to claim 1, feature are existed
In: described is one of liquefied ammonia, ammonium hydroxide, ammonium hydrogen carbonate containing ammonia liquid.
4. a kind of technique for being leached electrolytic manganese residues and manganese tailing using titanium white waste acid according to claim 1, feature are existed
In: the sulfide in the step 6) is manganese sulfide, and the fluoride in the step 6) is manganous fluoride.
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